Apparatus and process for converting refinery and petroleum-based waste to standard fuels

ABSTRACT

The present invention is an energy efficient method for separating petroleum-based waste including sludge, bottoms or used lubricants. By using solid particles and water, and converting them into useable end products, for example gas and gas/oil fractions. The process produces no wasteful by-products like polluted sewage, heavy asphaltenics and tar by-products. Instead, the process eliminates water through selective adsorption by dewatering additives and the process is followed by drying at high temperatures. The dewatering additives are recycled from other processes and are reusable themselves. After skimming the dewatered matter, the remainder is processed by thermocatalytic cracking. Some of the active materials in the cracking reaction are again waste products of other reactions. The gas and gas oil fractions obtained from this process conform to standard specifications. The process uses equipment that is cost-effective and that are routinely produced. The process and apparatus of the present invention provide a solution for processing refinery and petroleum-based wastes and production of useful and standard liquid fuels.

1. FIELD OF INVENTION

[0001] The present invention relates to the process of making a useable product out of refinery and other petroleum based sludge, bottoms and/or used lubricants with minimum environmental impact and to using waste of the type of slow moving emulsions and suspensions, containing organic matter and water with dissolved substances and suspended particles. The present invention also provides an apparatus for producing useful and standard fuels from refining and petroleum-based waste.

2. BACKGROUND

[0002] Finding a method to utilize refinery and/or other petroleum-based wastes, which represent, low mobility stable water emulsions with suspended solids, is a considerable problem. Currently available processes are costly, time consuming or high in waste by-products. A number of technologies have been described in the prior art.

[0003] U.S. Pat. 4,624,417 of Gangi, et al. discloses a method for converting sewage sludge into various energy sources such as steam or methane gas and non-energy by products such as cement board, gypsum fiberboard, and agricultural products.

[0004] U.S. Pat. 4,750,274 of Erdman, et al. discloses a method for bettering the sludge drying by means of large scouring particles addition. The scouring particles remove the particulate residue from the surfaces of heat exchanger, where the sludge is heated. The heat transfer is also intensified.

[0005] U.S. Pat. No. 4,897,205 of Landry is directed to petroleum sludge treatment by the use of steam and a re-circulating solvent with the purpose to decrease their viscosity and as a next step to separate the solid and the liquid components by settlement.

[0006] U.S. Pat. No. 4,927,530 of Ueda, et al. is directed to sludge treatment in the special tank by the use of anaerobic bacteria.

[0007] GB Patent 2218256 and U.S. Pat. No. 4,906,409 of Leister discloses a method in which sludge is dried in a fluid bed of preheated glass frit suspensed in nitrogen. The dried sludge and glass is conveyed pneumatically (by nitrogen) to the vitrification device.

[0008] U.S. Pat. No. 4,990,237 of Heuer, et al. discloses a method for oil recovery from waste oil sludge (pump-able, low viscosity, high oil and/or water-content sludge) by centrifugation of this type sludge. After that the centrifuge solids with low oil and water content are heated to volatize the contained water and oil. The oil and water are condensed and separated by settling. The separated oil is centrifuged again and refined; the solids can be disposed.

[0009] U.S. Pat. No. 5,022,992 of Looker discloses an apparatus for sludge separating by flotation for the floatable sludge.

[0010] U.S. Pat. No. 5,246,599 of Aicher discloses a method and arrangement for sewage sludge treatment in closed system, where the treatment steps are connected by continuous passages in a closed system. The sludge is dried, converted by 250-350° C. and finally sintered at least by 1250° C. The vapors removed in the drying stage and in conversion stage are condensed.

[0011] U.S. Pat. No. 5,259,945 of Johnson, et al. is directed to the bottom waste processing by means of the vapor rapid stripping and by treatment of the heavy part of waste in a pyrolytic reactor for producing vapors, gases and solid residue, which may be used as fuels.

[0012] U.S. Pat. No. 5,269,906 of Reynolds, et al. in addition to U.S. Pat. No. 4,990,237 of the same inventors calcium oxide is used for the active sludge neutralization and nickel settling by the sludge processing.

[0013] U.S. Pat. No. 5,271,851 of Nelson, et al. discloses a treatment system for refining oily sludge. The sludge is mixed with a particulate filter aid and with solvent selected from refinery products. The mixture contacts with a plate filter. A mixture of oil, water and solvent is produced as a filtrate. The filtrate is separated into an oil and water fraction. The oil fraction is directed to refinery. The produced water is routed to a refinery water treatment system. The filter coke residue is washed with a solvent, stripped to remove hydrocarbons and is removed for disposal.

[0014] U.S. Pat. No. 5,324,417 of Harandi discloses a method for refinery sludge and slop oils upgrading over hot equilibrium catalyst removed from FCC regenerator. The hot catalyst demetallized and/or demulsifies sludge and slop streams in an auxiliary reactor and converts the sludge and slop oil hydrocarbons to more light products.

[0015] U.S. Pat. No. 5,389,234 of Bhargava, et al. discloses a method for waste sludge disposal in a delayed coking process. In this order the waste at first is diluted with light hydrocarbons produced by delayed coking (naphtha or gas oil) to minimize fouling and foaming. The mixture stream is heated; the water and the light hydrocarbons are evaporated. The more heavy residue stream is heated to a coking temperature and is introduced into a coking drum.

[0016] U.S. Pat. No. 5,428,904 of Rutz discloses a method for drying sewage by a gas with temperature up to 50° C. The drying gas itself is reconditioned by reducing its moisture in a separate circuit and is returned to the start of the process. The gas-drying agent (a hygroscopic material) is regenerated by withdrawing moisture there from.

[0017] U.S. Pat. No. 5,466,383 of Lee is disclosed to treating dried sludge, also containing heavy metals. This process comprises indirectly heating the sludge in the absence of oxygen, up to temperature 300-550° C. for organic material volatilization and heating the residue up to 750-1000° C. together with steam for the non-volatile organic material gasification. The heavy metals remain in the ash as metal-sulfide complexes, which aren't soluble in acidic water.

[0018] U.S. Pat. No. 5,573,672 of Rappas, et al. discloses a process for separating extractable organic material intermixed with solids and water by dewatering the mixture with dehydration additives in common with organic solvent and following separation the organic solvent containing extractable organic material from the solids and hydrated additive.

[0019] U.S. Pat. No. 5,580,391 of Franco discloses a process for the thermo-chemical cleaning of storage tanks by combined action of an organic solvent and the generation of nitrogen gas and heat, whereby produced heating in city, agitation and flotation of the fluidized sludge and its transfer to tanks or desalting units. It is assumed the matter can be reintroduced after that in the usual refining flow.

[0020] U.S. Pat. No. 5,670,024 of Baltzer, et al. discloses a method for thermal treating of waste and residual material having coats of organic material by employing a drum-reactor developed for this process, heating the waste by a hot gas steam up to 850° C., evaporating and carbonizing the the organic material and completely combustion the material.

[0021] U.S. Pat. No. 5,681,449 and Japan Patent of Yokoyama, et al. discloses a method for treating an organic material containing solid sludge with water by means of heating the material up to 150-240° C. by pressure to obtain a fluidized sludge and processing the fluidized sludge up to 350° C. by 30-200 atm to convert the organic material to oil and after discharging separating oil from rest.

[0022] U.S. Pat. No. 5,827,432 of Huhtamaki et al. is directed to sludge dewatering by electrically ionizing or by ultrasound treating and adding coagulant to the sludge to effect coagulation.

[0023] RU Patent 2106313 of Fokin, et al. discloses a method of drying petroleum sludge under vacuum at heat carrier temperature 120-140° C. Drying is performed in three steps: stripping water and part of sludge hydrocarbons, continuously feeding organic solvent (toluene, gasoline fraction etc.) and stripping excess solvent.

[0024] U.S. Pat. No. 5,882,506 of Ohsol, et al. discloses a process for recovering oil from refinery waste emulsion by adding a sufficient amount of a light hydrocarbon diluent to the emulsion to lower its viscosity and specific gravity. The diluted emulsions are subjected to flashing at emulsion-breaking conditions after the oil is recovered.

[0025] U.S. Pat. No. 5,961,786 of Freel, et al. discloses a apparatus for a fast pyrolytic system. The feedstock, non-oxidative transport gas and inorganic particulate heated material are rapidly mixed, than transported upward through an entrained-bed tubular reactor. The system includes a cyclonic hot solids re-circulation system and the vapor quenching system.

[0026] From the used lubricants processing patents the following are more near to the proposed invention:

[0027] U.S. Pat. No. 4,342,645 of Fletcher et al. discloses a method of used lubricating oil re-refining by distillation to remove a volatile forecut and by further distillation with re-circulation to obtain the desired fractions of lubricating oil products while reducing the vaporization temperature. The recycle reduced coking and cracking. The used equipment is evaporator of three stage. The gasoline and the fuel oil are removed in the first and second stage evaporators. A light lube oil fraction is obtained then by distillation with a third stage wiped-film evaporator. A heavy lube fraction is obtained by distillation of the bottoms with evaporator too.

[0028] U.S. Pat. No. 4,435,270 of Audeh is directed to reclaiming usable stock from used lubricating oil by passing the used oil through a bed of oil shale. The shale removes impurities from the used oil. The shale is then heated to convert the kerogens to shale oil in the presence of hydrogen donor compounds contained in the lubricating oil remaining in the shale. These enhance hydrogen transfer during shale oil production.

[0029] U.S. Pat. No. 4,512,878 of Reid, et al. discloses a method for used-oil re-refining involving: heat soaking the used oil; distilling the heat soaked oil; passing the distillate through a guard bed of activated material; hydro treating the distillate guard bed treated under standard hydro treating conditions. If the used oil contained water and/or fuel fraction the used oil may be dewatered and defueled prior to heat soaked.

[0030] U.S. Pat. No. 4,833,185 of Fachini is directed to utilizing the sludge obtained from reclaiming lubricating oils by treating with acids or solvents. The sludge utilizing is proposed by the addition of elastomers and hardeners to obtain a compound usable in conjunction with bituminous conglomerates.

[0031] FR. Patent 2690924 of Digilio discloses a process for recycling of contaminated oil, particularly for re-processing lubricants comprises heating in autoclave reactor the used oil (lubricant) in common with added clarifier clay, 1-2% of water with dissolved S-based catalyst and 2% of filtration aid such on a diatonite. The heating temperatures are 100-150° C. and 300-320° C. for 2 hours. After that the product is distillated during 3 hours, filtered by pressure, treated repeatedly with clarified clay, catalyst in water, filtration aid and distillated.

[0032] DE. Patent 4240860 of Moskau is directed to creation apparatuses for physical-chemical treatment of used water-lubricant cooling emulsions, including a mobile cracking.

[0033] U.S. Pat. No. 5,384,037 of Kalnes discloses a process for production of hydrocarbons from waste lubricant by contacting waste lubricant stream with a hydrogen-rich gaseous stream in the flash conditions and producing a hydrocarbonaceous vapor stream comprising hydrogen, admixing the stream and contacting with a hydrogenation catalyst at hydrogenation conditions, production the hydrocarbon products.

[0034] U.S. Pat. No. 5,458,765 of West discloses a process of drying and removing solids from waste oil includes heating up to temperatures 180-200° F., adding of aqueous solution of carbodihydrazide and emulsifier. After that the precipitated solids and water are separated from the liquid hydrocarbon.

[0035] U.S. Pat. No. 5,582,271 of Mielo is directed to removing moisture, air and dirt from lubricating oil by apparatus contains two plates interposed and two flows of lubricant oil superimposed vertically by plates. The upper flow contains gas bubbles and the lower flow contains water and heavy particles. The two flows settle from water and heavy particles in a tank.

[0036] DE. Patent 19716436 of Matschiner is directed for used cooling lubricants reprocessing comprising: treating the lubricants with peroxo-di-sulphuric acid or their salts at 50-90° C., concentrating the sulphate-containing aqueous phase liberated from organics. The concentrate is used for electrochemical production of peroxo-di-sulphate and the water is recycled back to the process.

[0037] U.S. Pat. No. 5,672,277 of Parker, et al. discloses a method extraction of water by means of water-sorbing material that covers an inner surface of bag and presents in the bag as filaments.

[0038] U.S. Pat. No. 5,676,711 of Kuzara discloses a process of conversion used oil to a low-sulfur diesel fuel processing the used oil with coal as an oil-coal slurry by 850° F. and ˜100 atm in a time more than 1 hour.

[0039] U.S. Pat. No. 5,755,955 of Benham, et al. uses a hydrocracking process with preliminary addition to the feed coke as an inhibitor and iron compound.

[0040] U.S. Pat. No. 5,938,935 of Shimion discloses method and apparatus for purifying and treating cooling agents and/or lubricants used in the metallurgical industry. The solid particles are removed from the liquid by sedimentation on the plates, which are placed in specific manner, and additionally by magnetic force. U.S. Pat. No. 6,013,174 of Kovacs is directed to remove ash-forming contaminations from used oil by adding a demulsifier, heating up to temperature 190-200° F., separating the used oil in demulsified used oil, water and sediment layers, heating the demulsified oil up to 500-650° F., cooling the heat-treated oil, recycling 10-30% of this oil to demulsified used oil Gandi A. J. U.S. Pat. No. 4,624,417, Nov. 25, 1986; Erdman Jr. A., Johnson J. C., Levad J. A. U.S. Pat. No. 4,750,274, Jun. 14, 1988; Londry K. C. U.S. Pat. No. 4,897,205, Jan. 30, 1990; Ueda J. U.S. Pat. No. 4,927,530, May 22, 1990; Leister P. GB Paten. 2218256, Jun. 03, 1990; Heuer S. R., Reynolds V. R. U.S. Pat. No. 4,990,237, Feb. 5, 1991:; Looker J. U.S. Pat. No. 5,022,992, Jun. 11, 1991; Aicher M. U.S. Pat. No. 5,246,599, Sep. 21, 1993; Johnson, Jr., Satchwell R. M., Glaser R. R., Brecher L. E. U.S. Pat. No. 5,259,945, Nov. 9, 1993; Reynolds V. R., Heuer S. R. U.S. Pat. No. 5,259,906, Dec. 14, 1993; Nelson S. R., Claude A. M. U.S. Pat. No. 5,271,851, Dec. 21, 1993; Harandi M. N. U.S. Pat. No. 5,324,417, June 28, 1994; Bhargava A. K., Louie W. S. W., Stefani A. N. U.S. Pat. No. 5,389,234, Feb. 14, 1993; Rutz A. U.S. Pat. No. 5,428,904, Jul. 4, 1995; Lee K. U.S. Pat. No. 5,466,383, Nov. 14, 1995; Rappas A. S.; Paspek D. S. U.S. Pat. No. 5,573,672, Mar. 21, 1995; Franco Z. d., Khalil C. N., Pereira J. O. d. U.S. Pat. No. 5,580,391, Dec. 3, 1996; Baltzer F., Juptner H. U.S. Pat. No. 5,670,024, Feb. 6, 1995; Yokoyama Shinya, Kuiyagava Michio, Ogi Tomoko, Kebayashi Hideo, Minowa Towoaki, et al. U.S. Pat. No. 5,681,449, Jan. 11, 1996; Huhtamaki M., Lehtokari M., Paatero J. U.S. Pat. No. 5,827,432, Oct. 27, 1998; Fokin N. A., Kartashov M. V., Chemyshova N. E., Izmailov V. D. RU Pat. No. 2106318, Oct. 03,1998; Ohsol E. O., Pinkerton J. W., Gillispie T. E. U.S. Pat. No. 5,882,506, Mar. 16, 1999; Freel B. A., Graham R. G. U.S. Pat. No. 5,961,786, Oct. 5, 1999; Fleetcher L. C., Beard H. J. U.S. Pat. No. 4,342,645, Aug. 3, 1982; Audeh C. A. U.S. Pat. No. 4,435,270, Mar. 6, 1984; Reid L. E. Yao K. C., Ryan D. G. U.S. Pat. No. 4,512,878, Apr. 23, 1985; Fachini M. U.S. Pat. No. 4,833,185, May 23, 1989. (Foreign App. Priority Data—Jun. 4,1985 [IT], 21053A/85); Digilio V. A. FR. Pat. No. 2690924, Nov. 12, 1993; Moskau H. DE. Patent 4240860, Jun. 09, 1994; Kalnes T. N. U.S. Pat. No. 5,384,037, Jun. 29, 1993; West P. E. U.S. Pat. No. 5,458,765, Oct. 17, 1995; Mielo A. U.S. Pat. No. 5,582,271, Jul. 3, 1995; Matschiner H., Rehbock B. DE Pat. No. 19716436, Aug. 13, 1998; Parker S. C., Cubert R. M. U.S. Pat. No. 5,672,277, Oct. 17, 1994; Kuzara J. K., Klinger L. D. U.S. Pat. No. 5,676,711, Feb. 21, 1996; Benham N. K., Pruden B. B., Roy M. U.S. Pat. No. 5,755,955, Dec. 21, 1995; Shimion W. U.S. Pat. No. 5,938,935, Oct. 17, 1999; Kovacs G. L. U.S. Pat. No. 6,013,174, Jan. 11, 2000.

[0041] Thus, there are vast quantities of waste being produced worldwide that have the potential to be reused in a beneficial manner. The petroleum-based wastes can be processed to be used as gas and gas oil. There is a large niche in the market for the reuse of the intrinsically valuable waste stream. Efforts to develop a commercially viable resource recovery market have been hampered by problems of putrification and high levels of impurities. The key to establishing this market is to process the inputs of sludge and petroleum-based waste in a single process, not relying on transport of materials and making a uniform output that is not contaminating the environment in a secondary manner.

[0042] It is accordingly an object of the present invention to provide an efficient, inexpensive, process and apparatus for converting sludge waste into standard fuels.

3. SUMMARY OF THE INVENTION

[0043] It is an object of the present invention to provide a process for the conversion of petroleum-based waste containing water, organic matter and mineral particles to liquid fuels or their components conforming to standard specifications.

[0044] It is a further object of this invention to provide a process that includes a method for dewatering the materials without the formation of sewage, asphaltenic, or tar based wastes. The apparatus and process of the present invention have been described in detail by the accompanying figures, detailed description and specific embodiments of the invention below.

[0045] The primary object of this invention is to provide a process and apparatus able to handle variable waste loads in an economically viable manner.

[0046] It is another object of this invention to produce a useable fuel, mainly gas and gas oil.

[0047] It is another object of this invention to provide a process and apparatus to remove the water from some of the waste materials such as highly watered refinery sludge and still keep a low level of viscosity.

[0048] It is another object of this invention to provide a process and apparatus to remove the water without extracting the highly toxic compounds, thereby obviating the need to clean the contaminated water.

4. BRIEF DESCRIPTION OF THE FIGURES

[0049] The process of converting petroleum-based wastes into fuels includes the features of the invention depicted in the attached schematic drawings which form a portion of this disclosure, wherein FIG. 1 & 2 are flow diagrams detailing options of the process and FIG. 3 details the inner workings of the reactor for petroleum based waste processing.

[0050]FIG. 1 represent a flow diagram describing one embodiment of the apparatus and process of the present invention, and comprises of a dewatering mixer unit (1), a first sieve (2), a dryer (3), a reactor (4), a second sieve (5), a regenerator (6), a fractional column (7), a flow-forming chamber (8) and a blower (9).

[0051]FIG. 2 represent a flow diagram describing a second embodiment of the apparatus and process of the present invention, and comprises of a dewatering mixer unit (21), a first sieve (22), a reactor (23), a second sieve (24), a regenerator (25), a fractional column (26), a flow-forming chamber (27) and a blower (28).

[0052]FIG. 3. represents a diagram detailing the inner workings of the reactor for the petroleum-based waste, the reactor (41), comprising a heating jacket (42), a set of hoppers for the catalyst (43), a plurality of mixing elements (44), a petroleum-based waste charge pipe (45), a pipe for skimming vapors evacuation (46), pipes for cracking gases and vapors evacuation (47), pipes for cracking gases and vapors evacuation (48), a chamber for gas-vapor and solid product separation (49), a heat gas distribution pipe (50), and burners (51).

[0053]FIG. 4 and FIG. 5 show results which conform with the calculated results.

5. DETAILED DESCRIPTION OF PREFERRED EMBODIMENT

[0054] The invention provides the process of making a useable product out of refinery and other petroleum-based sludge, bottoms and used lubricants with minimum environmental impact. The treatment relates to the processing of slow moving emulsions and suspensions, containing organic matter and water with dissolved substances and suspended particles.

[0055] The overall process for treating the petroleum-based wastes comprises of the following steps:

[0056] a. removing the water by the use of solid grain dewatering materials derived from industrial waste or recycled materials (oil shale ash, FCC spent catalyst with the addition of lime, coal ash etc.);

[0057] b. removing the water from the petroleum-based waste by water selective sorption into the dewatering additives, as well as protection of the dewatering additives from contamination by oils by the controlled introduction of the additives in with the low moisture of the raw material and with the kinetics of the adsorption by the used additives;

[0058] c. recycling the dewatering additives while the adsorbed water is evaporated without expulsion thereby resulting in elimination of complicated and expensive equipment for the operation;

[0059] d. treating the vapors formed by dewatering by high temperatures in the catalyst regenerator;

[0060] e. skimming the process material by means of adding heat as well as heated catalytically active grain material;

[0061] f. decomposing the non-hydrocarbon components in the processed and/or used lubricants (different additives) and in the bottoms or slop with alkaline-earth components of the oil shale ash or with calcium oxide additives;

[0062] g. processing the remaining petroleum-based material in conditions conducive to catalytic cracking by interaction with the heated catalytically active materials;

[0063] h. mixing the resulting materials with additives including using as catalytic materials oil shale ash, FCC spent catalyst containing calcium oxide, or spent clays produced by treating clay with alkaline earth additives;

[0064] i. desulfurizing the matter produced in the previous step using the reactor being operated under the unique control of the present invention and;

[0065] j. utilizing a catalytically active material capable of regenerating and recycling in previous steps.

[0066] The petroleum-based sludges generally contain, up to 70% water. For example, in the samples that has been taken from sludge resevoirs at one refinery of the water content ranged within 57-68%. The sludge also contained 15-25% oil and 15-20% mineral particles. The lubricants generally contain moisture levels up to 5% water with mineral particles having a content up to 3%.

[0067] The sludge and used lubricants are stable oil-water emulsions and the mineral particles are suspended in the emulsions. The components of the sludge exhibit insignificant levels of settling, and therefore pose problems, for the dewatering step.

[0068] Current methods used for the separation of sludge mixtures include centrifugation, and organic matter extraction by solvent or flotation. These methods are expensive and create byproducts that are environmentally harmful. The water must be treated to remove impurities. Therefore the water evaporation method of the present invention is preferable, because it generates only pure steam, and not sewage, to be discarded into the environment.

[0069] Evaporation of the water from such a stable system as a petroleum-based waste is not possible by ordinary heating because of the strong interactions between the water/oil emulsions. For some more water-based used lubricants the evaporation method referred to herein as, “in moving thin layer” is acceptable, but for the sludge it is not suitable because of the high viscosity of the materials. However, these alternative methods described in the art are both expensive and inefficient.

[0070] An additional problem regarding the use of dewatering materials is that once the dewatering materials and petroleum-based waste are mixed, both the water and oils are adsorbed. As a result the water adsorption capacity of the dewatering additives is decreased and after several cycles becomes negligible. To regain the adsorption capacity, dehydrating materials (CaO, CaCl₂, Al₂O₃, silica gel, etc.) are added to watered material and mixed. However, these dehydrating materials rapidly lose the ability to adsorb, and at the same time, cannot be recycled. Hence, the overall consumption requirement for dehydrating materials is increased.

[0071] The present invention bypasses these problems by creating a situation of selective adsorption of the water from the oil emulsion, while simultaneously utilizing inexpensive and reusable materials, by using solid dewatering recyclable grain materials.

[0072] The present invention is able to achieve selective adsorption due to the adsorption kinetics of the water and oil components. The adsorption capacity and rate is higher for the water component than for the oil component. So if the dewatering additive is linked to a variable feed mechanism then the optimal rate of application can be calculated. The advantage of this is that all of the additives are not applied at once and the water will be completely adsorbed while the oil layer persists untouched. The dewatering material can then be introduced depending on the program developed and is changed by varying the screw-feeder rotation speed.

[0073] The present invention also provides the procedure to determine the adequacy of a given material as a dewatering additive by the petroleum-based processing. To be considered as a suitable additive the materials must be shown to have been created as a by-product of another process. These by-products include:

[0074] oil shale ash; oil shale coke-ash residue after the oil shale thermal processing—half-coking or retorting, gasification, etc.;

[0075] granules from by-product of coal mining mixed with bentonite or clay; or

[0076] spent clays from the clay-treatment in refineries useable after regeneration in the present process.

[0077] Modified bentonite, marls, sepiolite, grain materials and some cellulose-contained materials that are formed in the presence of an oxidant are suitable and are of low cost. These and other like materials adsorb not only water selectively, but also oils. However, the selective absorption of water can be achieved by the procedure of the present invention.

[0078] The oil shale ash adsorption capacity to water is 65-70% on the mass. The oil shale coke-ash residue adsorbs up to 55% water.

[0079] The grain material Sepiolsa (98%, 0.5-6.0 mm) includes sepiolite 80%, dolomite 15%, other materials 5% and sorbs up to 90% water.

[0080] When the dewatering grain material granularity ranges within 1.0-6.0 mm that allows for separation of the material from the dewatered raw matter, and its mineral particles. The size of the mineral particles in processed petroleum-based waste is generally smaller than 100 μm. Therefore, variants of the conditions of the dewatering stage can be used depending on the dewatering material granularity.

[0081] Variant 1: the dewatering material is coarser than the mineral component in the raw material and is separated after the water adsorption

[0082] In this case the dewatering material is introduced into the mixer in a controlled manner, where the petroleum-based waste is located, and the water is adsorbed under suitable conditions (i.e. temperature). The mixture then consists of coarse dewatering particles impregnated by water, and the dewatered raw material. If the raw material is sludge, the dewatered matter has two components, the mineral (the sludge mineral particles) and oil component. The mineral-oil particles can stick together and form small aggregates. But the aggregates aren't durable and easily break up. In any event all particles can be efficiently separated from the aggregates by sieving (using a wire sieve) due to the consistent particle size of 1 mm. The experiments have shown if the dewatering particles size is 1.5-2 mm and more they can be separated without problem.

[0083] A raw material, which is a liquid lubricant, the matter represents a mixture of coarse dewatering particles saturated by water, and the dewatered liquid oil with dispersed small particles. The dewatering material particles are easily separated from dewatered oil.

[0084] If the oil component is very viscous the water adsorbing stage must take place under conditions with temperatures up to ˜50-60° c.

[0085] After the dewatering the petroleum-based raw material is directed to the following processing. The dewatering material is directed into a jacketed dryer, dried and recycled to the raw material ready to be used again to dewater.

[0086] The steam formed during drying is directed into the catalyst regenerator and is treated there at a temperature of ˜750° C. The organic substances, which can be captured by steam (contained in the adsorbed water and other) are decomposed and burned at this temperature. The amount of captured organic substance by this operation does not equal more than 0.5% of the total. This mechanism may be used to successfully remove the organic based wastewater in form of pure and disinfected steam therefore avoiding the expulsion of the watered matter by the heating process.

[0087] Variant 2: the dewatering material cannot be separated after the water adsorption and heating in common dries all matter. This procedure of drying also nins without the danger of the expulsion of matter by heating, because of the adsorbed water evaporation from solid particles. In this case the water-oil emulsion is destroyed by water adsorption prior to evaporation. This separation of the emulsion is the key to successful evaporation.

[0088] During the drying process the steam formed contains organic vapors at concentrations in the range of 1-2%, which are then directed into the catalyst regenerator. Here they are burned, and reused, giving additional heat to the process.

[0089] This procedure can be used for example if the dewatering material is oleo-phobic. In this case the dewatered petroleum-based matter is heated up to higher temperatures. Consequently, this saves heat in the next stage of processing. After the mixture has undergone heating and drying, the coarse dewatering material is separated by sieving, and once again recycled for water removal. The operations of mixing and drying can be carried out in one mixer-dryer with jacket heating.

[0090] This procedure is also used if the dewatering material is not needed in large amounts because it does not disturb the subsequent processing of the dewatered raw matter while in catalytic cracking conditions.

[0091] The present invention provides procedures in which the oil shale ash and the coke-ash residue are catalytically active under hydrocarbon catalytic cracking conditions. The natural combination of the aluminum silicate matrix with calcium oxide creates the catalytic activity. Therefore the oil-shale ash used as a dewatering material can also be dried in common with the raw material. In the later stages it is used as a catalytically active material, being heated up to 450-500° C. and then separated after the cracking process.

[0092] Variant 3: the dewatering material is finely grained and cannot be separated from the dewatered raw matter particles.

[0093] This procedure is possible if the dewatering material is also catalytically active and can be used as a catalyst on the next stage of the process. This material, as in the previous example, can be the oil shale ash. The dewatering and catalytically active material is mixed (under controlled conditions) with the petroleum-based waste, the water is then adsorbed by the dewatering material, then the whole mixture is heated up to the drying temperature, and subsequently the dewatering material is directed into the reactor.

[0094] After the dewatering stage the reactor processes the raw material. The reactor carries out several operations as enumerated below.

[0095] The raw material is skimmed in conditions depending on the process objectives. If the objective is to produce maximum gasoline yield, the cut off point for heating is up to 210° C. and after that the residue is cracked. If the objective is to produce maximum gas-oil yield the cut point is 350° C.

[0096] The heat for the skimming is provided by the addition of the required amount of the hot catalyst. In this case the catalyst serves as a direct heat carrier. If a surplus of heat is formed in the regenerator, (by sufficient cracking coke yield) the matter to be skimmed is jacket heated by the regenerator flue gases.

[0097] After skimming the treated matter is transported (by means of the mixing elements of the reactor) into its activation zone. The hot catalyst is added into the activation zone for mixing at temperatures of 350-380° C. At this stage the lubricant additives and acidic sulfur and oxygen compounds of the sludge are decomposed.

[0098] The activated matter is then transported into the cracking zone where it is treated by the catalyst at a temperature appropriate for catalytic cracking. The preliminary adsorbing of the organic matter into the catalyst grains, and the subsequent activation of matter, increases the intensity of the temperature, thereby reducing the heat consumption of the process.

[0099] The vapors and gases formed move out from the reactor and enter into the vortex chamber where they are cleaned to remove the captured catalytic dust. The dust is directed into catalyst regenerator and recycled to cracking process.

[0100] The cleaned vapors and gases are separated by means of the fractional column, the gases are cooled, and the vapors condensed and cooled.

[0101] The catalyst with the addition of formed coke (that deposits in the catalyst grains) is removed from the reactor by means of the same mixer elements performing the task of both mixing and discharging. The removed catalyst is directed into the fluidized bed regenerator, where the coke is burned out, and the catalyst grains are heated up to 750° C. The regenerated and heated catalyst is recycled to the raw materials, to act as a catalyst and as a heat-carrier.

[0102] Suitable catalytically active materials are generally spent materials from other processes such as: oil shale ash, FCC spent catalyst, sweet clays, and spent clays after processing the sludge with a series of specially prepared materials, including a silica-alumina, and calcium oxide containing additives. Presence of the calcium oxide also helps with the decomposition of the additives in the lubricants and to neutralizing and decomposing of the acidic components that may be present in the petroleum-based sludge and waste.

[0103] The optimum mixture combines the oil shale (as a catalytic active material) with the silica-alumina (up to 30%), and calcium oxide and carbonate. This composition makes it possible to carry out the thermo-catalytic cracking and to also prevent the sulfur oxide emission (into the atmosphere), by the coke burning out in the catalyst regenerator. This combination allows for the greatest speed of the chemical reaction while still considering environmental safety.

[0104] The acid sprayed clays (and in particular the activated montmorillonite acid) are useful materials for the catalytic cracking. The activated zeolite granule acid is also suitable for the cracking process. When there are substantial amounts of heavy metals in the oil, a silica-alumina FCC catalyst in mixture with activated clays, is found to absorb the metals. In the case of processing sludge that contains a great amount of fine mineral particles, the coarse catalytically active materials are used. They can be separated from the sludge dust during the sieving stage, after the reactor stage, or after the regenerator stage, depending on the success of removing the sludge mineral component.

[0105] The dust mineral component of a refinery sludge coated with coke (after the reactor) was tested with a positive result as a substance useful to the cement industry. Its coke gives an added heat in the cement kiln, and its particles size and composition (SiO₂, Al₂ O₃, CaO, Fe₂O₃, etc.) are acceptable for cement production. It is clear that the dust and coarse catalyst separation after cracking process are suitable for this alternative application, when the dust particles are coated with the coke. In other cases it is reasonable to burn out the coke in the dust to use the dusty minerals depending on their composition and properties as filling or covering materials, etc.

[0106] When processing used lubricants the dusty mineral component amounts to less than 2-3%. The mineral component contains metals and metals oxide particles, and after their separation from the catalyst they can be used in metallurgy.

[0107] The gases formed during sludge processing basically contain hydrogen, hydrocarbons, hydrosulfide and a very small amount of carbon monoxide and dioxides. All of the gases are burned in the catalyst regenerator. If the oil shale ash is used as a catalytic active material the sulfur oxide formed by the burning of H₂S (like by the coke burning) is caught by the calcium oxide and calcium carbonate contained within in the oil shale ash. The emission of sulfur oxide emission is prevented by using a plant (20 kg/h) operated at temperatures of 750-800° C. in the regenerator. In other cases the materials containing calcium carbonate are added to aid in the trapping of the SO₂. Their presence, positively affects the cracking process and the desulfurization of the formed fuels. The heat created from the burning gases increases the heat potential of the process, where part of the heat obtained in regenerator is used for raw material dewatering.

[0108] In FIGS. 1 and 2 the flow diagrams of the process are shown differing one from another by the variants of the dewatering stage.

[0109] Referring to FIG. 1 the watery petroleum-based waste (sludge, etc.) is mixed with the dewatering additive, which is introduced by the controlled regime into horizontal mixer 1 with paddle mixing elements and jacket heating possibility. After the water adsorption by the additive grains the matter is separated by the wire sieve 2, into coarser dewatering grains and other matter that looks to be in the case of sludge, as small mineral particles oiled by petroleum based material. The dewatering grains are dried by the jacket heating dryer-mixer 3 and recycled to the raw material dewatering stage. The formed vapors are directed in the catalyst regenerator 6.

[0110] The second variation in FIG. 2 shows the vapors formed in the dewatering mixer 21 can be directed to the regenerator 25 if the sludge is dewatered and the drying temperature is 100-150° C. If the temperature is more than the or if waste is comprised of used lubricant oil and dewatered, the formed vapors are directed to the system of condensation, cooling and oil-water separation. The separated water is treated in the catalyst regenerator 25.

[0111] The dewatered sludge or lubricant is directed into reactor 4 (FIG. 1). The reactor is a horizontal mixer with paddle mixer and discharge elements (FIG. 3). It is equipped with heating jacket 42 (FIG. 3) and system able to control hot catalyst introduction 43. The system consists of a bunker and screw feeder with variable rotation speeds to three heating zones of the reactor. The catalyst-feeding regulator controls the screw feeder rotation speed, which corresponds to the temperature in each appropriate zone.

[0112] In the first zone skimming the petroleum-based material is carried out with cut off point up to 350° C. As a rule this is controlled by means of the added hot catalyst. The vapors are evacuated through the fractional column 7 (FIG. 1) that separate two fractions: (a) up to 210° C. (gasoline) and (b) up to 350° C. (gas oil).

[0113] In the second zone the non-hydrocarbon component are decomposed (such as additives in the lubricants, etc.) and the activation of all remaining reaction matter (catalyst impregnated by remainder of the processed material) is carried on. Furthermore, the hot catalyst is also added as a direct heat carrier.

[0114] In the third zone of the reactor the catalytic cracking of the remaining material is carried out and the formed vapors and gases are evacuated through the fractional column

[0115] The coke covered catalyst and mineral part of the processed sludge are discharged from the reactor 4 by the same mixer elements and are separated by means of sieves 5 (FIG. 1). The catalysts that are coarser are directed to the fluidized bed regenerator and from there is recycled to the reactor. In some cases the dusty mineral part of the processed material, also coke covered, is not separated from catalyst and is directed into the regenerator. After the coke is burned out, the catalyst and the mineral components of the process material are separated.

[0116] The flue gases from the regenerator 6 are evacuated through the cyclone or vortex chamber that cleans the gases from the dust more effectively. The flue gases heat is utilized for processing of the dewatered materials and the reactor.

[0117] The petroleum-based waste processing can be organized as a batch process. Its advantage lies in the ability of the process to carry on the basic operation on the principle of “all operation in one reactor”. It means by one jacket heated reactor-mixer the dewatering stage can by carried out, and after production of enough of the dewatered matter, thermal processing (skimming, reaction matter activation, catalytic cracking) can be realized in the same reactor (one after another). Only the catalyst regenerator must be operated in continuous regime of treating the coke-covered catalyst accordingly to the reactor output (the reactor must provide for the catalyst feeder-bunker). The batch process is convenient for the small plants processing 2-3 tons per hour on the basis of raw materials formed in the concrete region.

6. EXAMPLES

[0118] The equipment used for the process development and testing includes:

[0119] a laboratory reactor 0.5 liters volume with the stationary layer;

[0120] bench-scale unit with the horizontal, batch, heat reactor-mixer volume 7.5 liters, equipped by paddle mixer-elements suitable for the raw material dewatering, skimming and cracking;

[0121] a pilot plant including the horizontal heat reactor-mixer, volume 45 liters, (the sludge processing capacity is ˜20 kg/h), suitable for the raw material dewatering, skimming and catalytic cracking.

Example 1

[0122] Processing of the refinery sludge with the composition, (mass %): water 59.2 organic matter 24.9 solids 15.9.

[0123] The metal content in the ash from the sludge, (mass %) is: vanadium 0.2 nickel 1.1 iron 12.3 silicon 7.45 aluminum 10.71 sodium 1.31 calcium 14.7.

[0124] The oil shale ash was used as a dewatering additive and as a catalytically active material.

[0125] The oil shale ash composition, (mass %) is: SiO₂ 16.0 MgO 1.1 Al₂O₃ 7.9 Na₂O 0.3 Fe₂O₃ 3.3 K₂O 0.6 CaO 64.8 SO₃ 1.7

[0126] Oil shale ash has a water adsorption capacity of 64.9%.

[0127] This oil shale adsorption of ash consumption of the sludge was 91.2%.

[0128] The sludge dewatering was carried out in a batch regime feeding the sludge, which allows for reliable water selective adsorption during the controlled introduction of the dewatering grain matter.

[0129] In the batch mixer, with jacket heating, and an operating volume of 45 liters the sludge volume of 22 liters was input. The oil shale ash-feeding regime had been estimated on the basis of the water adsorption kinetics and the mixing regularity investigation.

[0130] The experiments for the adsorption kinetics determination showed the time of saturation point of the grain material can be assumed 10 sec. That timeframe is well below that of the mixing time of the dewatering matter and the sludge. Therefore water at the point of contact between the grains and the sludge runs readily, and the total sludge dewatering rate and hence time, depends solely on the rate and time of achieving an effective mixture.

[0131] Based on experimentation with different grain materials, it was found that the cell (zone) model is suitable for a mathematical description of the materials flow. The total volume (of the mixer) can be represented as a series cell with individual types of flow in each cell. For the distribution process in the cells the Markov's chains is employed. Assuming all cells have equal volumes V_(i) and the material passed through them at a rate Q then:

Q _(1,2,) =Q _(2,3) =. . . =Q _(m,i),

[0132] where Q_(1,2), Q_(2,3)—volume rate transfers from one cell to another. Each group of particles located in the i_(th) cell will stay in it, until it transfers to the next one along the flow cell (i+l).

[0133] Expected results have a good coincidence with the obtained results (40, 41) (the predicted mixing time for Heterogeneity Coefficient=1% is 4.81 min and the experimental optimum is 5 min by 76 r.p.m. Curtus W. Clump. Mixing of solids Pp. 263-287; practice, vol. II, Charter 10. Edited By Vincent W. Uhl, 1967; an Cheremisinof N. P. Mixing of granular and loose solids. In Encyclopedia of fluid mechanics, vol. 4, pp. 61-109. Gulf Publishing Company, USA, 1985.

[0134] Since the water adsorption runs at a high rate, the dewatering process is assumed to consist of two conditional stages:

[0135] the water adsorption occurs in the zone of the dewatering grain material introducing;

[0136] the dewatered petroleum-based matter and the dewatering grain material saturated by water are transferred by the mixing elements from the first zone into the other mixer volume. In this “other volume” the dewatered matter and the water-saturated grains are mixed with the remaining non-dewatered matter and a new water concentration is obtained. The new concentration is invariably lower than it was before the dewatering process began. Also formed is a new volume of total dewatering matter.

[0137] The partially dewatered matter of the new water concentration enters into the first zone. In this zone the dewatering sorbent must be introduced in sufficient amounts that conform to a new water concentration. However, it is important to only add amount of the dewatering additive that will adsorb considerably less than necessary to completely adsorb all the water. This will ensure that the adsorbent is readily saturated by water and will not adsorb any of the oil present.

[0138] The dewatering process calculation algorithm is presented below.

[0139] Notation: Q_(s)(t) volumetric throughput of the [1/sec] dewatering adsorbent Q volumetric throughput during [1/sec] mixing (between zones) T process time [sec] V₁(t) volume of zone i [1] V(t) = V₁ + V₂ total reactor volume [1] C₁(t) H₂O concentration in zone i

[0140] Assumptions: 1. The sludge contains 60% (vol.) of H₂O. 2. The adsorbent is capable of adsorbing 65% of H₂O (mass). Therefore, the adsorbent bulk density 0.7 should be taken into consideration when calculating the effective volume percentage of adsorption. It will be assumed therefore that the adsorbent is capable of adsorbing 45.5% of H₂O (vol). 3. The adsorption is assumed almost immediate (during 10 sec. most of the possible volume of H₂O is adsorbed). 4. According to (2), the total volume of adsorbent to be injected into the mixer in order to adsorb at least 99% of the H₂O contained in the sludge is (60%:

[0141] 45%)100=133.3% of the sludge volume. 5. The adsorbent throughput is decreased linearly from an initial value of (Q_(s,0) to 0 so that the total volume of the injected adsorbent would constitute 133.3% (vol.) of the sludge (90% of the sludge mass). Q_(s)(t) are a continuous-time volumetric throughput function (the discretization is precise, since

<<T), and its integral on [0, T] determines the total volume of the injected adsorbent.

[0142] According to (5), Q_(S)(t) is a linear function of the form:

[0143] Q_(S)

V₀

at

[0144] where a determines the injection throughput decrease rate and V₀ is the initial injection throughput.

[0145] From the stated condition the following equation is obtained: ^(T) ₀

1.33V $\frac{1}{2}{{Tv}_{0} \cdot 1.33}V$

[0146] A technologically feasible value of VO should be selected, and the resultant process time (T) can then be obtained accordingly. Also worth noting, T must be a reasonable processing time, depending on desired capacity.

[0147] The following equation describes the process (assuming discrete time with interval

between measures): $C_{1}{\cdot \frac{C_{1}V_{1}QC_{2}C_{1}0.455Q_{s}}{V_{1}}}$ $C_{2}{\cdot \frac{C_{2}V_{2}QC_{1}C_{2}}{V_{1}}}$

[0148] where: C₁(t)=the water concentration change; C₂(t)=the dewatering sorbent concentration change.

[0149] (All the percentages are assumed volumetric)

[0150] If

_(S)

is the volume of the inserted adsorbent (in a time unit t), the adsorbed volume 0.455

_(S)

should not exceed the appropriate current water volume in order to avoid the adsorption of organic components contained in the sludge.

[0151] If for some reason the stated condition does not hold, the volume of the oiled adsorbent (which has adsorbed a certain volume of organic components) can be easily calculated.

[0152] Let V_(W)(t) be the volume of water in zone 1 (it is determined from the concentration C₁(t) and the volume V₁(t)). Assume that

S; V_(W)

0.455

_(S)▪0, i.e. the condition does not hold for a certain set of time points S.

[0153] The total volume of the oiled adsorbent is obtained by the following discrete sum (which can be approximated by a continuous-time integral): V_(oiled) 

V_(W)(t)

0.455

₁(t)

[0154] It is obvious that the selection of the parameters a V₀ and T influences the Volume of oiled adsorbent. Larger T values would result in less V_(oiled); however the reasonable process time should be selected.

[0155] In most cases, including the given example, there exist such parameters that the process time is reasonable and the minimum oiled adsorbent volume is at most 1% of the injected one.

[0156] In other cases, the linear function Q_(s)(t) can be replaced with a non-linear (e.g. an exponential) one with respective parameters. For our example: Q_(s)(t) 0.0163 − 4.515 · 10⁻⁶ · t [1/sec], Q 0.083 [1/sec] T 3600 [sec] Δ 1 [sec] V_(1,0) 5.5 [1] V_(2,0) 16.5 [1] V₀ 22 [1]

[0157] where: V₀=0.0163 is calculated from the equation ½TV₀=1.33V. If T=3600 sec, V=22 liters, V₀ ${V_{0} \cdot \frac{1.33222}{3600} \cdot 0.0163};$

[0158] 0.0163;

[0159] the coefficient a=4.515 10⁻⁶ is calculated from equation a · V 0

[0160] graphic solution; the quantity 0.083 1/sec is the volume rate conforming with the mixing parameters by the heterogeneity coefficient 1% and the mixing time 5 min;

[0161] T=3600 sec conform to the hour capacity;

[0162] Δ=1 sec is the agreed interval of discrete time between measures.

[0163] V_(1,0)=5.5 liters—initial sludge volume in the injection zone 1;

[0164] V_(2,0)=16.5 liters—initial sludge volume in zone 2;

[0165] V₀=22 liters—initial total sludge volume.

[0166] The zones of the total charge volume (22 liters) are selected to maintain a ratio of V₁: V₂=1:4.

[0167] The experimental results presented in FIG. 4 and FIG. 5 showed conformity with the calculated results. So, the dewatering adsorbent introduced according to the calculated regime, shows the final water concentration to be 1.2% (suitable for the next processing), and is achieved with oil absorption of only ˜0.1%, which falls inside the error limits.

[0168] After the dewatered stage all the matter was discharged from the mixer, and the sieving mechanism separated the dewatering additives. The water saturated oil shale ash was dried by means of the reactor-mixer jacket heating.

[0169] The dewatering vapors were directed into catalyst regenerator. The same operation was repeated with the second sludge portion. The separated two portions of the dewatered sludge were charged into the reactor-mixer and heated up to 350° C. by the addition and mixing of the catalytic active material, which was previously heated up to 750° C. It was assumed that the catalytically active material heated the oil shale ash. The catalytically active material had a granularity of 1.4-2.8 mm. By heating the mixture up to 350° C. the oil component was skimmed successfully.

[0170] The remained reaction matter was activated by temperatures of 375° C. (by added hot catalyst) and was catalytically cracked by the addition of the next portion of the catalytically active material (oil shale grains) heated up to 750° C. The catalytic cracking average temperature was 480° C.

[0171] The product yield was, mass %: water 59.2 oil 19.4 solid product 18.5 (mineral particles coke covered including 2.7% of coke) other “carbon” 0.1 gas 2.7.

[0172] The produced oil properties Properties Produced oil Density (15° C.) 0.904 Viscosity (50° C.), cSt 3.9 Sulfur 0.4 HHV, kcal/kg 10683 Water content 0.2 Ash — Stability 2 Metals content, ppm: Vanadium (V) 0.00 Nickel (Ni) 0.00 Aluminium (Al) 0.00 Hydrargyrum (Hg) 0.00 Plumbum (Pb) 0.00

[0173] The produced oil conforms to standard for final oil of type light mazout.

Example 2

[0174] Processing of the used automotive lubricant with composition, mass %: water 1.6 tars 3.0 ash 1.1 (unsolubles metals 0.03 in benzene) asphaltenes 12.5 density (15° C.) 0.909 (unsolubles viscosity (40° C.) 60.5 in n-pentane) sulfur, % 0.43

[0175] For the used lubricant dewatering, Sepiolsa (sepiolite 80%, dolomite 15%, others 5%) was used as a dewatering additive. Its bulk density is 0.65 kg/liter, 0.5-6 mm is the grain size of 98% of the particles. Sepiolsa is not selectively water adsorbent and under ordinary conditions adsorbs oil as well. Therefore, controlled introduction was applied. The dewatering process calculation was carried out by the same algorithm that by Example 1, also taking into consideration the other properties of Sepiolsa. The mixer (with a volume of 45 liters) was charged with 30 liters of the used oil. After the completion of the dewatering stage the water concentration in the used oil was 0.2% and the oil content in the sorbent was ˜0.1%.

[0176] The watered Sepiolsa was separated from the oil by sieve and dried. Its adsorption capacity was not affected due to the drying and reuse.

[0177] The dewatered used lubricant was charged in the same reactor-mixer and skimmed using temperatures up to 350° C. (by means of added FCC E-catalyst with admixed 5% of the treated clay preliminary heated in the catalyst regenerator up to 750° C.).

[0178] The remaining reaction matter (the catalyst impregnated by the material) was activated by temperatures of 350° C. The next step uses the regenerator FCC E-catalyst with admixed regenerated spent clay (750° C.), which is added to the reaction matter and the remaining used lubricant material that was cracked in catalytic cracking conditions. The liquid phase cracking residence time was five minutes, the vapors average contact time with the catalyst was four seconds

[0179] The product yield was, mass %: water 1.6 oil 85.2 gas 6.5 coke 5.6 minerals 1.1.

[0180] The produced gas oil properties are: density (15° C.) 0.868 metals, ppm: viscosity (40° C.), cSt 3.3 phosphorus 0.00 sulfur 0.1 calcium 0.00 distillate up to 92.2 magnesium 0.00 357° C. zinc 0.01 HHV, kcal/kg 10817 V, Ni, Cr 0.00

[0181] Although the present invention is described in connection with particular preferred embodiments and examples, it is to be understood that many modifications and variations can be made in the process and apparatus without departing from the scope to which the inventions disclose herein are entitled. Accordingly it will be understood that these embodiments are illustrative and that the scope of the invention is not limited to them. The present invention is to be considered as including all apparatus, systems and methods encompassed by the appending claims. 

What is claimed is:
 1. A process for treating petroleum-based waste feed containing organic matter, water, soluted substances or solid particles, said process comprising the steps of dewatering the waste, and producing high value fuels or components and having negligible outputs of polluted water, asphaltenes and tar.
 2. The process according to claim 1, wherein the dewatering process comprises of the steps of: a) Adding sufficient amounts of dewatering grain material to the feed, b) Mixing and removing the water without contaminating the dewatering material by the petroleum components.
 3. The process according to claim 2 wherein the dewatering materials are more coarse than the feed particles and the the process further comprises the steps of: a) separating by a sieve said feed particles from the dewatered petroleum-based matter, b) drying the dewatered material with steam is directed into a catalyst regenerator at a temperature of 750° C., and c) recycling the dry materials.
 4. The process according to claim 1, wherein the dewatered petroleum-based material is heated to 350° C. in a heat reactor-mixer by the addition of a hot, catalytically active material.
 5. The process according to claim 1, wherein the dewatered material is heated by the addition of a hot catalyst, the reaction matter activation and the decomposing of non-hydrocarbon components is accomplished by healing at 350-380° C.
 6. The process according to claim 5, further comprising catalytic cracking of the reaction, removing the dewatered solid material, separating, condensing and cooling the vapor and gaseous products and reusing the dewatered material.
 7. The process according to claim 5, further comprising burning of the gases in the catalyst regenerator, and catching of the formed sulfur oxide by the alkaline-earth components.
 8. The process according to claim 7 further comprising removing the catalytic material from the reactor and regenerating the catalyst and flue gases.
 9. The process according to claim 8, further cleaning the flue gases for reuse.
 10. The process of claim 1 wherein the feed includes tank bottom waste, refinery slop or other refinery sludge.
 11. The process of claim 1 wherein the feed consists of used lubricants.
 12. The process of claim 1 wherein the dewatering and catalytic active material includes oil shale ash or grain materials of the oil shale ash modification.
 13. The process of claim 1 wherein the dewatering materials include marls, modified bentonite, sepiolite grain materials, “Sepiolsa”—grain material 0.5-6 mm, containing sepiolite 80%, dolomite 15%, by-product of coal mining mixed with bentonite or clay; material on basis of cellulose modified or grained in mixture with bentonite.
 14. The process of claim 10 wherein the dewatering material is not separated from the petroleum-based matter and the total mixture is heated for the sorbed water evaporation.
 15. The process of claim 11 wherein the dewatering material is not separated from the petroleum-based matter and the total mixture is heated for the sorbed water evaporation.
 16. The process of claim 14 wherein the temperature of the mixture for water evaporation is up to 200° C. and the light hydrocarbons are distilled with steam, further comprising the steps of condensing the vapors, separating the liquid hydrocarbons from the water, and directing the water into the generator for evaporating and burning any remaining organic matter.
 17. The process of claim 1 wherein the catalyst active material for the catalytic cracking includes grain oil shale ash or the regenerated oil shale coke-ash residue.
 18. The process of claim 1 wherein the catalytic active material for the the catalytic cracking are the FCC catalysts with addition of limestone (1-20%).
 19. The process of claim 3 wherein the catalytic active material for the catalytic cracking includes the spent clay or the FCC catalyst with the treated spent clay (1-10%).
 20. The process of claim 1 wherein the dewatering of the petroleum-based waste is done in combination with the suitable solid additives in the reactor mixer. 